Preparation of acetone-soluble fibrous nitroacylate



nitroacylate directly: soluble in' acetone may be prepared by the use ofa liquid oxide of nitrogen in a suitable solvent. -The time ofacylation, for instance acetylation, may be four hours or even less.:However, it'has .CYRIL J. swam) enn RUSSEL 1-1. VAN

Patented Jul 11, 1933 IPA- EN? see or eocnrsrnaimw YORK, assrenons ToEASTIVIANYKOED'AK COMPANY, OF ROCHESTER, NEW YORK, A CORPQR-ATION OF NEWYORK -I rnnrnn arxort or 'AOETGNE-SOLUBLE rrnnons NETROAGYLATE' NoDrawing. p

Our invention relates to the production of an acetone-soluble'fibrouscellulose nitroacylate by treating a eellulosic material with a fattyacid anhydnde and itllqlllCl oxlde of nitrogen in an organic liquidwhich is a non solvent {such as carbon tetrachlorlde), for

the cellulose esters which may be present in the reaction mass. r

The processes usually employedin the commercial manufactureof-fcellulose acetate action of the acetic anhydride whichmay be presenttherein and to likewisehydroly'ze the cellulose acetate. There are a'reat number of processes for efiecting this result;

Manufacturers of cellulose acetate have realized for some time that if acommercial process could be (lGVlSBd to'prepare cellulose acetate in thefibrous form and solublein acetone, considerable economy in. the cost ofproducing thisester would result. In the patents and literaturethere areprocesses described for the hydrolysisfof chloroform soluble fibrouscellulose acetate, but none of them have proven to besufiiciently'economieal nor result in a product.of suff1ciently goodquality for commercial application.

en-object of the; present invention is to' provide a process forobtaining fibrouscellulosenitroacetate, soluble in acetone. Anotherobjectlof the invention is to provide a process of producing this acetonesoluble fibrous cellulose nitroacylate by one acylation operationvwithout" the necessity of hydrolysis. Processes heretofore carried outhave involved first, either acetylating the cellulose and then nitratingit, or acetyla-ting cellulose nitrate. :However, there have been someprocesses ,which permitted ,of' a. simultaneous acetylation-Eandnitration of cellulose, but

none ofthese have contemplated the use of the effective nitrating agentwhich comes within the realm of our nvention We have now found thatfibrous cellulose Application filed December 31, 1930. 'Se' ria1 1 To505,967 I :f.

ting together, and gives a clear viscous solutil complete acetylatio.

'cial acetic acidxand 2 cc of 1 z-gn'lixer consisted approximately. ofthe 'follo been found that if the acetylation is allowed to run for 24hours or even longer improved solubility, results. Theprodu'ct is inexcellent fibrous form without any lumps or mattion in acetoner 1 i nefollowing examplesillustrative of this inrention apply to thepreparationof acetone- 'SOlLlblG-fllll'OllS nrho-acetate;

. Emamplel I 'About 50 grams of'co'tton linters were treated with aboutgrains ofglaci'alvacetic acid and 2 cQcI' of l :3 n'1ixedcatalystlsul-vl phuric and phosphori c acids respectively) at roomtemperature for 14-20 hours; Thismixturc may thenbepressed off to aweight of about 150 grams and cooled down about C; To this pressed "maswas added a mixture consisting ofabout 120cc of 95% acetic anliydridemadeup 50'2100115450 c.c.

with carbon tt3tl .0lll01lil. Before mixing With the anhydride, about lOc.'c. otliquid nitrogen dioxide was added to the] carbr "1tetrachloride. Y These added materials were n'iixedthoroug with thepretreated linters I and the tempe 1 hie bath was brought up to 5O C i:i 'aboutihours, and the mixturewas .eld at this temperature unhad takenplace. This caneasilybecompleted in 3-5 hours.

However, it. is preferred thatthe operation be continued for a longertime. (The fibrous cellulose nitrate acetate thus produced was -a foundto be soluble inacctone. V

Emample ll j s I vAbout grams ofc'otton linteis were treated with annrtture'o'f about 350 granrsbfighlystat room temperature,as in the pexample. After this pie-treatment the is drained off and the lintersniay' be wasl two or three times with cairbon tetrachl and allowed todrain. The remainin Aceticacirh l Carbon tetrachloride The masswas.cooled and about 1220 etc; of

% acetic anhydride Was'added; This was immediately followed by additionof 'abou cc ofcarbon tetrachloride containingap g stood that other fattyacids and fatty acid proximately 10 cc. of liquid N and the Qtrogen usedas the nitrating agent.

whole was thoroughly mixed. The temperaanhydrides may be usedinstead'ofthe acetic compounds to produce the corresponding fibrouscellulose nitroacylate. Thus, by the use of butyric acid, or aceticacid, and butyric anhydride, instead of the acetic anhydride, a fibrouscellulose nitro-acetate-butyrate or cellulose nitro-butyrate may beformed.

' It is to be understood that other acetylation catalysts may beusedcinstead of the phosphoric-sulphuric mixture: As various acetylationcatalysts are well known in the art,

enumeration of them is believed unnecessary. Also, in place .of carbontetrachloride, other organic solvents of like nature may be used in thisacetylation such as carbon bi-sulphide,

trichloroethylene, petroleum distillate, toluol and the like.

It is also to be noted thatwe may either press oil or washout thepretreating acid from the cellulose prior to acetylation and nitration.Obviously any known method of pressing may be employed and numeroussolvents for acetic acid may be used to wash it out of the cellulose.The requirement 'is merely that the acetic acid present he reduced to areasonably small amount so that the acylate produced will be retained inthe fibrous formby the non-solvent organic liquid added. A r

WVha-t we now claim as our invention and desire to secure by LettersPatent of the United States is:

1. A process of making a fibrous-cellulose nitrate-acylate whichcomprises treating cellulose with a fatty acid anhydride and a -liquidoxide of nitrogen having a boiling point greater than 0C. in an organicliquid in which the cellulose ester is insoluble.

2. A process of making a fibrouscellulose nitrate-acylate whichcomprises, treating cel-' lulose with a fatty-acid anhydride and aliquid oxide of nitrogen having a boiling point greater than 0 C. incarbon tetra chloride. V i V A process of making a fibrous cellulosenitrate-acetate which comprises treating cel- The lulose with aceticanhydride in carbon tetrachloride.

12. A process of making a'fibrous cellulosenitrate-acetate whichcomprises treating "cel- N05 in carbon-tetrachloride.--

lulose with acetic anhydride and a liquid solvent for cellulosenitrate-acetate.

5. A process of making a, fibrous cellulose nitrate-acylate in a liquidbath-which comprises treating cellulose with a fatty acid anhydride anda nitrating agent selected from the group consisting of N0 N 04, N 0 andN 0 in an organic liquid in which the cellulose ester is insoluble.-

61A process of. making. fibrous cellulose nitrate-acetate whichcomprisestreating cellulose with acetic anhydride and'aliquid nitratingagent selectedfrom the-group consisting of N 0 N 0 N 05 and N 0 in anorganic liquid which is anon-solvent for cellulose nitrate-acetate, c7.. A process of making 3;:filJIOL1S cellulose nitrate-acylate whichcomprises treating cellulose with a fatty acid anhydride and liquid N 0in anorganic liquid'in which the cellulose esteris insoluble.

8. A process of, making a fibro'us cellulose nitrate-acylate whichcomprises treating cellulosewith a'fatty acid anhydride and liquid N0incarbon tetrachloride;

9. A. process of making a fibrous cellulose nitrate-acetate whichcomprises treating cellulose with acetic-anhydrideand liquidzNO in anorganic liquidwhich is anon-solven for cellulose nitrate-acetate.

10. A process of making a fibrous cellulose nitrate-acetate whichcomprises treating cellulose with acetic anhydride and liquid N0 in arelativelylargeamount of an organic liquid which is a non-solvent forcellulose nitrate-acetate. A V

11. A process of making a fibrous-cellulose nitrate-acetate whichcomprises treating celand liquid N0 lulose with acetic anhydrideandliquid N0 in an amount of carbon tetrachloride more than six timesthe weight .ofthe cellulose. I

13. A process ofmaking-a fibrous cellulose nitrate-butyrate which icomprises treating cellulose with butyrie anl'iydride and liquid Signedat Rochester, New York. 7

' r "RUSSEL-H. vA N- DYKE.

GYRIL JJSTAUDL'

